Water-insoluble acetoacetylamino benzimidazolone monoazo dyestuffs



United States Patent 3,328,384 WATER-INSOLUBLE ACETOACETYLAMINOBENZIMIDAZOLONE MONOAZO DYE- STUFFS Erich Dietz, Kelkheim, Tannus, andKarl Schilling, Frankfurt am Main, Germany, assignors to FarhwerkeHoechst Aktiengesellschaft vorrnals Meister Lucius & Bruning, Frankfurtam Main, Germany, a corporation of Germany No Drawing. Filed Apr. 9,1964, Ser. No. 358,623 Claims priority, application Germany, Apr. 18,1963, F 39,512 3 Claims. (Cl. 260-157) The present invention providesnew, valuable waterinsoluble monoazo dyestuffs; more particularly, itrelates to water-insoluble monoazo dyestuffs of the general formula inwhich the group R-HNO S- is in metaor paraposition to the azo group, Rrepresents a hydrogen atom, an alkyl, hydroxyalkyl, alkenyl, aralkyl orcycloalkyl radical or an aryl radical which may be substituted bynon-ionogenic radicals, and benzene nuclei B and C may be substituted byalkyl groups, alkoxy groups or halogen atoms.

The present invention is based on the observation that new, valuablewater-insoluble monoazo dyestuffs can be prepared by coupling thediazonium compounds of amines of the general formula in which the groupRHN-O S is in metaor paraposition to the amino group, R represents ahydrogen atom, an alkyl, hydroxyalkyl, alkenyl, cycloalkyl or aralkylradical or an aryl radical which may be substituted by non-ionogenicradicals, and benzene nucleus C may be substituted by alkyl groups,alkoxy groups or halogen atoms, with the acetoacetyl compounds of 5-arninobenzimidazolones which may be substituted in the benzene nucleusof the benzimidazolone radical by alkyl or alkoxy groups or halogenatoms.

The monoazo dyestufis obtained according to the proccess of the presentinvention may be prepared by combining the solution or suspension of thediazo compound with the coupling component present in a weakly acidmedium in finely dispersed form or by adding the alkaline solution ofthe coupling component to the solution 0r suspension of .the diazocomponent first introduced into the reaction vessel and adjusted to apH-value of 5 to 6 by an addition of sodium acetate. Another possibilityof carrying out the coupling is to add the solutionor suspension of thediazo component and the alkaline solution of the coupling componentsimultaneously to a butter mixture of sodium acetate and acetic acid.The coupling may be effected in the presence of anionic, cationic ornon-ionogenic surface-active agents.

In order to attain the optimum grain structure of the pigments and toimprove their fastness to solvents it is expedient, When the coupling iscomplete, to heat the dyestuif suspension for some time, possibly in thepresence, of small amounts of organic solvents such as methanol,ethanol, chlorobenzene, dichlorobenzene, dimethylformamide, pyridine orquinoline, if desired even to temperatures above 100 C. under pressure.Another kind of after-treatment consists in stirring the aqueousdyestulf press cake or the dried dyestuff for some time, possibly in theheat, in suitable organic solvents, for example methanol, ethanol,chlorobenzene, dichlorobenzene, formamide, dimethyl formamide, N-methylacetamide, dimethyl sulfoxide or pyridine. According to the method ofafter-treatment applied a change in shade can be observed which is dueto a change in th estructure of the crystals.

The new pigments are suitable for the preparation of printing colors andcolor lakes as well as for the dyeing of caoutchouc, natural resins andpolymerization and condensation plastics. Moreover, the dyestutfprepared according to the process of the present invention may be usedfor the dyeing in the spinning mass and for the dyeing or printingaccording to the usual pigment dyeing or printing processes.

As compared with known monoazo dyestuifs of the acetoacetic anilideseries which are not derived from the acetoacetyl compounds of theS-aminobenzimidazolones, the new pigments are distinguished,.in additionto a very good fastness to light and a very good resistance to Weather,by an improved fastness to solvents, which is evident in all theproperties connected with the fastness to solvents, as for examplefastness to oil, overnpraying, overvarnishing, blooming and bleeding.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to the liter.

- Example 1 21.6 parts of 1-arnino-2-methoxybenzene-5 sulfonic acidmethyl amide are diazotized in 300 parts by volume of ice water and 60parts by volume of 5 N-hydrochloric acid with 20 parts by volume of 5N-sodium nitrite solution and the diazo solution is made up to 750 partsby volume by adding ice water.

Moreover, 24.5 parts of S-acetoacetylamino-benzimidazolone are dissolvedin 150 parts by volume of 2 N- sodium hydroxide solution and 600 partsby volume of water.

While stirring vigorously, the two solutions are simultaneously added,drop by drop, during about 30 minutes and at approximately the samespeed to a butler mixture consisting of 250 parts by volume of Water,parts by volume of 4 N-sodium acetate solution, parts by volume of 2N-acetic acid and 15 parts by volume of a 10% aqueous solution of theproduct obtained by reacting 1 mol of oleyl alcohol with 30 mols ofethylene oxide.

When the coupling is complete the mixture is heated for one hour to90-95 C. by introducing steam, the dyestull formed is filtered withsuction, washed with water and dried.

There are obtained 46 parts of a reddish yellow pigment dyestutl, whichis heated to the boil for one hour in 600 parts by volume of ethanol inorder to improve its grain structure. It is then filtered with suction,washed with ethanol and dried. The pigment obtained has an excellentfastness to light as well as a very good fastness to solvents,overspraying and bleeding.

Example 2 been prepared in the following manner: 24.5 parts ofS-acetoacetylamino-benzimidazolone are dissolved in 150 parts by volumeof 2 N-sodium hydroxide solution, and the solution is diluted with 600parts by volume of water. After having added 100 parts by volume of 4N-sodium acetate solution and 25 parts by volume of a aqueous solutionof oleylamine acetate the coupling component is precipitated, whilestirring vigorously, by adding 150 parts by volume of 2 N-acetic acid.

After having introduced the diazo solution, 30 parts by volume ofpyridine are added and, when the coupling is complete, the mixture isheated for one hour to 9095 C., by introducing steam. Subsequently, thedyestuff is filtered with suction, washed with water and dried.

The yield amounts to 50 parts of a reddish yellow pigment dyestuifhaving a very good fasteness to light as Well as a good fastness tosolvents and migration.

Example 3 26 parts of 1-amino-2,5-dimethoxybenzene-4-sulfonic acidethylamide are diazotized in 300 parts by volume of ice water and 60parts by volume of 5 N-hydrochloric acid with 20 parts by volume of 5N-sodium nitrite solution and the diazo solution is made up to 750 partsby volume by adding ice Water.

Moreover, 24.5 parts of S-acetoacetylamino-benzimidazolone are dissolvedin 150 parts by volume of 2 N-sodium hydroxide solution and 600 parts:by volume of water.

The two solutions are simultaneously introduced, drop by drop, whilevigorously stirring, during about 30 minutes and at approximately thesame speed, into a buffer mixture consisting of 250 parts by volume ofwater, 100 parts by volume of 4 N-sodium acetate solution, 150 parts byvolume of 2 N-acetic acid and 15 parts by volume of a aqueous solutionof tbeproduct obtained by reacting 1 mol of oleyl alcohol with 10 molsof ethylene oxide.

When the coupling is complete the mixture is heated for one hour to 9095C. by introducing steam, the dyestutf formed is filtered with suctionand washed with water. Subsequently, the moist dyestulf press cake isstirred with a small amount of water to yield a homogeneous paste, andafter having added 100 parts by volume of ethanol the mixture is heatedunder pressure for 3 hours to 125130 C. The product is then once morefiltered with Diazo Component Coupling Component Tintl-aminobenzene-El-sultonic acid 5-acetoacetylamino- Yellow.

methylamide. benzimidazolone.

1-aminobenzene-4-sultonic acid d0 Do.

methylamide.

1-amino-2-methylbenzene-E- c .do Reddish snltom'c acid amide. yellow.

1-amino-2-methylbenzene-S- do Do.

sulionic acid methylamide.

1-amino-2-methy1benzene-5- .do D o.

sulfonic acid benzylamide.

l-amino-Z-chlorobenzene-fi- -do Yellow sulfonic acid amide.

1-amino-2-chlor0benzene-5- .do c D o.

sultonic acid methylamide.

1-amino-2-chlor0bcnzene-5 .do Do.

sulfonic acid anilide.

l-amino-Z-methoxybenzene-5- ,do Reddish sulionic acid ethylarm'de.yellow.

1-amino-2-methoxybenzene'fi- .do D o.

sultonic acid ethanolamide.

l-amino-2-methoxybenzene-5- d0 D o.

sultonic acid-i-propylamide.

1-arnino-2-methoxybenzene-5- .do D 0.

sulfonic acid-n-butylamide.

1-aininoQ-methoxybenzene-S- do D0.

sulfonic acid benzylamide.

1-amino-2-rnethoxybenzene-5- do Yellow.

snlfonic acid cyclohexylamide.

l-amino-Z-niethoxybenzene-5- .do Reddish sultonic acid allylamide.yellow.

Diazo Component Coupling Component Tint 1-amino-2-methoxybenzene-5- doDo.

sulionic acid anilide. 1-amino2methoxybenzene-fido D0.

sulfonic acid-2-methy1anilide. 1-amino-2-methoxybenzene-5- d0 Do.

sulfom'c acid-i methylanilide. 1-amino2-rnethoxybenzene-5- .do D0.

sultonic acid-2-chloroanilide. 1-amino2methoxybenzene-5- d0 Do.

sulfonic acid-4-chloroanilide. 1-amino-2-methoxybenzene-5' d0 Yellowsulfonic acid-3-methoxyanilide. l-amino-Z-methoxybenzene-5- do Do.

sulfonic acid-4-methoxyanilide. 1amino-2-methoxybenzene-5- d0 Reddishsulfonic acid-2-chloro-5- yellow. methylanilide.1-amino-2-methoxybenzene5- .d0 Yellow.

sulfonic acid-2,5-dichloroanilide. 1-amin0-2-methoxy-4-chlorod0 D0.

benzene-S-sultonic acid ethylamide. 1-amino-2-meth0xy--methyldo Do.

benzene-5-sultonic acid ethanolamide. 1-arnino-4-chlorobenzene-S-sul-..do Reddish ionic acid benzylanu'de. yellow.1-amin0-2,fi-dimethoxybenzenedo Yellow.

4-sulionic acid amide. 1-amino-2,5 dimethoxybenzenedo D0.

4-sulfonic acid methylamide. 1-amino-2,5-diethoxybenzenedo Do.

-sulfonic acid ethylanu'de. l-arnino-2,5dimethoxybenzene- .d0 Do.

4-sulfonie acid ethanolamide. l-amino-Z,5-diethoxybeuzene-4- d0 Do.

sulfonic acid ethanolamide. 1-amiuo-2.5-dimethoxybenzenc- .do Do.

4-sulfonic acid-n-butylamide. 1-amino-2,5-dimethoxybenzene- ..do Do.

4-sulfonie acid allylamide. 1-amino-2,5-dimethoxybenzenedo Do.

4-sulfonic acid anilide. 1-amin0-2,5-dimetlioxybenzene- .d0 Do.

4-sultouic acid cyclohexylamide. 1-amino-2,5-dirnethoxybenzene- -d0 Do.

4-sulfonic acid 2-methylauilide. 1-amino-2,5-dimethoxybenzenedo Do.

4-su1tonic acid 4-chloroanilide. 1-amino-2-methoxy-5chlorodo Do.

benzeneA-snltonic acid methylamide. l-amino-2-methoxy5-chloro- .do Do.

benzene-l-sulfonic acid ethanolamide. l-amiuo2-methoxy-5-methyl- -do Do.

benzene-4-sulfonic acid ethylamide. l-amino-2-methoxy-5-methyl- .do D o.

benzene-*i-sultonic acid benzylamide. 1-amino-2,5-dichlorobeuzenc-4- doDo.

sultonic acid methylamide. l-aminobenzene-3-sulfonic acid5-acetoacetylamino- Do.

amide. 6-chloro-benzimidazolone. l-arninobenzene-3-sulfonic acid --.doDo.

ethylamide. Lamino-Z-chlorobenzene-5- -.do- D0.

sulfonic acid amide. 1-amino-2,fi-dirnethoxybenzeue- .d0 Do.

e-sulfonic acid ethylamide. l-aminobenzene-3-su1tonic acid5acetoacetylamino-7- Do.

amide. chl0ro-beuzimidazolone. l-aminobeuzeue-B-sulfonic acid d0 Do.

cyclohexylamide. l-amiuo2-methylbe11zene-5- do Do.

sulionic acid benzyl amide. l-amino-Z-methoxybenzene5- do Do.

sulfonic acid amide. l-amino-Z-methoxybenzene-5- .do- Do.

sulfonic acid anilide. 1-amino-2-chlorobenzene-5- d0 Do.

sultonic acid amide. 1-amino-2,5-dimethoxybenzenedo Do.

4-su1fonic acid ethanolamide. l-amino-Z,E-dimethoxybenzenedo Do.

4-sulfonic acid anilide. l-amino-Z-methoxybenzene-5-5-acetoacetylarnino-7- D0.

sulfonic acid amide. bromo-benzimidazolone. l-amino-Z-chlorobenzene-5-5-acetoacetylamino-6- Do;

sultonic acid amide. methyl-benzimidazolone. l-amino-Z-methoxybenzene-5-.do Do.

sulionic acid allylamide. 1-amino-2,5-dimethoxybenzene- ..do Do.

4-sulionic acid methylamide. l-amin0-2,5-dimethoxybenzene- -do Do.

4-su1tonic acid ethanolamide.

1. A WATER-INSOLUBLE MONOAZO DYESTUFF OF THE FORMULA 